Sulfur-contaminated ionic liquid catalyzed alklyation

Abstract

A sulfur-contaminated ionic liquid catalyst is provided comprising 300 to 20,000 wppm of sulfur from a contaminant, wherein the catalyst is a chloroaluminate and it alkylates olefin and isoparaffin to make an alkylate gasoline blending component having a FBP below 221° C. A process is provided for making the alkylate gasoline blending component, comprising: a. feeding olefin feed comprising greater than 80 wppm of sulfur contaminant to a chloroaluminate ionic liquid catalyst, to make a sulfur-contaminated catalyst; and b. alkylating olefin feed with isoparaffin to make the alkylate gasoline blending component. A method to construct a refinery alkylation unit is provided comprising installing an ionic liquid alkylation reactor having an inlet that feeds a pure coker LPG olefin. An alkylation process exclusively utilizing coker LPG olefins is also provided.

It is claimed: 
     
         1 . A sulfur-contaminated ionic liquid catalyst, comprising 300 to 20,000 wppm of a sulfur from a sulfur contaminant, wherein the sulfur-contaminated ionic liquid catalyst is a chloroaluminate and the sulfur-contaminated ionic liquid catalyst can alkylate an olefin and an isoparaffin to make an alkylate gasoline blending component having a final boiling point below 221° C. (430° F.). 
     
     
         2 . The sulfur-contaminated ionic liquid catalyst of  claim 1 , comprising 1,000 to 10,000 wppm of the sulfur. 
     
     
         3 . The sulfur-contaminated ionic liquid catalyst of  claim 1 , wherein the sulfur contaminant comprises sulfur species found in coker olefin feed. 
     
     
         4 . The sulfur-contaminated ionic liquid catalyst of  claim 1 , wherein the sulfur contaminant comprises sulfur species formed during treatment of a hydrocarbon feed with a selective adsorbent that dries the hydrocarbon feed. 
     
     
         5 . The sulfur-contaminated ionic liquid catalyst of  claim 1 , wherein the sulfur contaminant comprises mercaptans, alkyl sulfides, and alkyl disulfides. 
     
     
         6 . The sulfur-contaminated ionic liquid catalyst of  claim 1 , comprising a metal halide. 
     
     
         7 . The sulfur-contaminated ionic liquid catalyst of  claim 1 , comprising an ammonium, a phosphonium, or a sulphonium cation. 
     
     
         8 . The sulfur-contaminated ionic liquid catalyst of  claim 1 , comprising N-butylpyridinium chloroaluminate. 
     
     
         9 . A process for making an alkylate gasoline blending component, comprising:
 a. feeding an olefin feed comprising greater than 80 wppm of a sulfur contaminant to a chloroaluminate ionic liquid catalyst, wherein a level of the sulfur contaminant accumulates in the chloroaluminate ionic liquid catalyst to make a sulfur-contaminated ionic liquid catalyst comprising 300 to 20,000 wppm of a sulfur from the sulfur contaminant; and   b. alkylating the olefin feed with an isoparaffin using the sulfur-contaminated ionic liquid catalyst to make the alkylate gasoline blending component having a final boiling point below 221° C. (430° F.).   
     
     
         10 . The process of  claim 9 , wherein the olefin feed comprises C3 and C4 olefins. 
     
     
         11 . The process of  claim 9 , wherein the olefin feed comprising the sulfur contaminant comes from a refinery and comprises 100 to 1000 wppm of organic sulfur species and at least 20 wt % C3 and C4 olefins. 
     
     
         12 . The process of  claim 9 , wherein the olefin feed comprising the sulfur contaminant is dried using a selective adsorbent. 
     
     
         13 . The process of  claim 9 , wherein the sulfur contaminant comprises mercaptans, alkyl sulfides, and alkyl disulfides. 
     
     
         14 . The process of  claim 9 , wherein the olefin feed comprising the sulfur contaminant is a coker LPG stream comprising: 
       
         
           
                 
                 
                 
               
                     
                 
                     
                   Components 
                   Wt % 
                 
                     
                 
                     
                   Propane (C3) 
                   10.0-25.0 
                 
                     
                   Propene (C3=) 
                   4.0-8.0 
                 
                     
                   Isobutane (iC4) 
                    6.0-12.0 
                 
                     
                   n-Butane (nC4) 
                   25.0-40.0 
                 
                     
                   1-Butene (1-C4=) 
                    8.0-11.0 
                 
                     
                   2-Methylpropene 
                    5.0-10.0 
                 
                     
                   (iC4=) 
                     
                 
                     
                   trans-2-Butene (t- 
                   3.0-7.0 
                 
                     
                   2-C4=) 
                     
                 
                     
                   Cis-2-Butene (c- 
                   2.0-5.0 
                 
                     
                   2-C4=) 
                     
                 
                     
                   1-3-Butadiene (1- 
                   0.0-1.0 
                 
                     
                   3-C4DE) 
                     
                 
                     
                   Isopentane (iC5) 
                   0.5-5.0 
                 
                     
                   n-Pentane (nC5) 
                   0.0-1.0 
                 
                     
                   C5+ 
                   1.1-3.0 
                 
                     
                   Total 
                   100.0 
                 
                     
                   Total C3= 
                    4.0-12.0 
                 
                     
                   Total C4= 
                   18.0-30.0 
                 
                     
                   Total Olefins 
                    22.0-42.0. 
                 
                     
                 
             
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         15 . The process of  claim 9 , wherein the chloroaluminate ionic liquid catalyst comprises an ammonium, a phosphonium, or a sulphonium cation. 
     
     
         16 . The process of  claim 9 , wherein the alkylating is performed continuously for one to 365 days. 
     
     
         17 . The process of  claim 9 , wherein the final boiling point is from 191 to 207° C. (376 to 404° F.). 
     
     
         18 . The process of  claim 9 , wherein the isoparaffin comprises isobutane. 
     
     
         19 . The process of  claim 9 , additionally comprising continuously sending a portion of the sulfur-contaminated ionic liquid catalyst to a regeneration reactor to regenerate the sulfur-contaminated ionic liquid catalyst and to maintain 0.5 to 10 wt % of a conjunct polymer in the sulfur-contaminated ionic liquid catalyst during the alkylating. 
     
     
         20 . A method to construct a refinery alkylation unit, comprising: installing an ionic liquid alkylation reactor comprising an ionic liquid catalyst and wherein the ionic liquid alkylation reactor comprises an inlet that feeds a coker LPG olefin to the ionic liquid alkylation reactor without mixing the coker LPG olefin with other olefin feeds such that the coker LPG olefin makes a sulfur-contaminated ionic liquid catalyst; wherein the coker LPG olefin comprises from greater than 80 to 500 wppm of organic sulfur species and at least 20 wt % C3 and C4 olefins; and wherein an effluent from the ionic liquid alkylation reactor comprises an alkylate gasoline blending component having a final boiling point below 221° C. (430° F.). 
     
     
         21 . The method of  claim 20 , additionally comprising installing a drier unit comprising a selective adsorbent that dries the coker LPG olefin between an effluent port of a coker unit and the inlet that feeds the coker LPG olefin to the ionic liquid alkylation reactor. 
     
     
         22 . The method of  claim 20 , additionally comprising replacing an existing HF or H2SO4 alkylation reactor with the ionic liquid alkylation reactor. 
     
     
         23 . An alkylation process exclusively utilizing coker LPG olefins, comprising:
 a. treating a coker LPG stream containing olefins with an amine treater, a caustic treater, or a combination thereof, to produce a treated coker LPG stream having a total sulfur content from 80 to less than 500 wppm and a total mercaptans content from 10 to 150 wppm,   b. drying the treated coker LPG stream to produce a dried coker LPG stream having from zero to less than 1 wppm water, from zero to 20 wppm total mercaptans, greater than 80 wppm total sulfur, and from zero to less than 100 wppm total oxygenates;   c. feeding the dried coker LPG stream, unmixed with any other olefins, and an isobutane to an alkylation reactor containing an ionic liquid catalyst, wherein the ionic liquid catalyst becomes a sulfur-contaminated ionic liquid catalyst; and   d. alkylating the olefins with the isobutane using the sulfur-contaminated ionic liquid catalyst to make an alkylate gasoline blending component having a final boiling point below 221° C. (430° F.).